CN115722198A - Preparation and application of metal ion doped aminated lignin-based dye adsorbent - Google Patents
Preparation and application of metal ion doped aminated lignin-based dye adsorbent Download PDFInfo
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- 239000003463 adsorbent Substances 0.000 title claims abstract description 48
- 238000002360 preparation method Methods 0.000 title abstract description 7
- 229910021645 metal ion Inorganic materials 0.000 title description 4
- 239000000975 dye Substances 0.000 claims abstract description 103
- 238000001179 sorption measurement Methods 0.000 claims abstract description 74
- 239000003513 alkali Substances 0.000 claims abstract description 32
- 125000002091 cationic group Chemical group 0.000 claims abstract description 30
- 238000003763 carbonization Methods 0.000 claims abstract description 11
- 125000000129 anionic group Chemical group 0.000 claims abstract description 10
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 claims abstract description 5
- 229910001431 copper ion Inorganic materials 0.000 claims abstract description 5
- 238000000034 method Methods 0.000 claims description 54
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- 229960001124 trientine Drugs 0.000 claims description 3
- LRWZZZWJMFNZIK-UHFFFAOYSA-N 2-chloro-3-methyloxirane Chemical compound CC1OC1Cl LRWZZZWJMFNZIK-UHFFFAOYSA-N 0.000 claims description 2
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 claims description 2
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- OARRHUQTFTUEOS-UHFFFAOYSA-N safranin Chemical compound [Cl-].C=12C=C(N)C(C)=CC2=NC2=CC(C)=C(N)C=C2[N+]=1C1=CC=CC=C1 OARRHUQTFTUEOS-UHFFFAOYSA-N 0.000 abstract description 18
- RBTBFTRPCNLSDE-UHFFFAOYSA-N 3,7-bis(dimethylamino)phenothiazin-5-ium Chemical compound C1=CC(N(C)C)=CC2=[S+]C3=CC(N(C)C)=CC=C3N=C21 RBTBFTRPCNLSDE-UHFFFAOYSA-N 0.000 abstract description 17
- 229960000907 methylthioninium chloride Drugs 0.000 abstract description 17
- STZCRXQWRGQSJD-GEEYTBSJSA-M methyl orange Chemical compound [Na+].C1=CC(N(C)C)=CC=C1\N=N\C1=CC=C(S([O-])(=O)=O)C=C1 STZCRXQWRGQSJD-GEEYTBSJSA-M 0.000 abstract description 11
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- 150000001450 anions Chemical class 0.000 description 2
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Abstract
The invention relates to a preparation method and application of a metal copper ion doped aminated lignin-based cationic dye adsorbent. The preparation of the lignin-based cationic dye adsorbent mainly comprises the following steps: amination and carbonization of alkali lignin and copper ion doping. Compared with the prior art, the copper ion doped aminated lignin-based adsorbent prepared by the invention can efficiently adsorb cationic dyes such as safranin T, azure B, methylene blue and the like (the adsorption capacities are 1420, 1168 and 787mg/g respectively), and can selectively adsorb the cationic dyes in a mixture of the dyes and an anionic dye methyl orange (the selectivity coefficients are 32, 198 and 103 respectively).
Description
Technical Field
The invention belongs to the technical field of water treatment adsorption materials, and particularly relates to a lignin-based cationic dye adsorbent, and a preparation method and application thereof.
Background
Organic dyes are a class of aromatic compounds and are widely used in the textile, paper, leather and other industries. Most organic dyes are stable in chemical structure, difficult to degrade and toxic to some extent, can damage the stability of an aquatic ecosystem and harm aquatic organisms and human health. Different physical, chemical and biological methods have been explored for the treatment of organic dye wastewater in industry. The adsorption method is still the most widely used organic dye wastewater treatment method in industry at present due to the advantages of easy operation, no sludge and no harmful intermediate. Common organic dye adsorbents comprise metal nanoparticles, metal organic framework materials, activated carbon and the like, and generally have the advantages of large specific surface area and large adsorption capacity, however, the development of the adsorbents is severely limited by the remarkable limitations of difficult synthesis, high cost, non-renewable precursors and the like. With the proposal of a 'double-carbon' target, the efficient, environment-friendly and renewable dye adsorbent prepared by green energy has more application value.
The lignin is an aromatic high-molecular compound with the largest reserve in nature, has rich oxygen-containing functional groups, can form pi-pi conjugation, electrostatic force and other interactions with organic dye molecules, and is an adsorbent raw material with huge potential. Metal oxide loading, graft copolymerization, carbonization and the like are common methods for increasing the adsorption amount of lignin. In the prior art, CN201910819256 uses lignin metal ion doped aminated lignin for adsorption of As (V) anions in water. In the aspect of dye adsorption, CN201410733512 uses metal oxide loaded aminated lignin for adsorbing metal ions and dye (the adsorption capacity of aniline blue is 499.75 mg/g); CN202110751213 uses magnesium nitrogen doped lignin for adsorbing methylene blue (adsorption capacity is 200 mg/g), and has the disadvantage of low adsorption capacity. In addition, although the aminated lignin disclosed in CN202010086952 can strongly adsorb anionic dyes (the adsorption capacities of amino black 10B and reactive red 120 are 2647.3 and 2533.8mg/g, respectively), the adsorption has no selective effect, and selective adsorption of specific ionic dyes in an anion and cation mixed solution cannot be performed.
The invention constructs Cu-N on aminated lignin by doping copper ions x The obtained adsorbent not only has high adsorption capacity (1420, 1168 and 787mg/g for the adsorption capacity of safranine T, azure B and methylene blue respectively) for cationic dyes, but also shows high-efficiency selectivity (selectivity coefficients are 32, 198 and 103 respectively) for the cationic dyes in the binary dye mixture of the cationic dyes and the anionic dyes of methyl orange, and can realize rapid adsorption for the cationic dyes.
Disclosure of Invention
The invention aims to provide a preparation method of a dye adsorbent and the dye adsorbent prepared by the method, the method is low in cost and strong in repeatability, the obtained dye adsorbent is obvious in effect, green and environment-friendly, and high-valued utilization of waste resources is realized.
Another technical object of the present invention is to provide the use of the dye adsorbent for preparing a mixture for separating cationic dyes.
In one aspect, the present invention provides a method for preparing a lignin-based dye adsorbent, the method comprising the steps of:
(1) Aminated lignin can be purchased or made in-house. The self-making can adopt the following amination steps:
dissolving alkali lignin in an alkali solution to obtain an alkali lignin solution, dropwise adding epoxy chloropropane to react the mixed system, dialyzing to be neutral, filtering and drying to obtain an epoxidation intermediate. Adding polyamine dropwise into the prepared epoxidation intermediate, heating for reaction, filtering, washing and drying to obtain aminated lignin;
(2) A carbonization step:
carbonizing the aminated lignin obtained in the step (1);
(3) Copper doping: the carbonized aminated lignin obtained in the step (2) is mixed with N, N-Dimethylformamide (DMF) and copper dichloride (CuCl) 2 ) Mixing, heating under the protection of inert gas for reaction, cooling to room temperature, washing with a detergent, and drying to obtain the dye adsorbent.
In a specific embodiment, in step (1), the alkali lignin is an industrial alkali lignin, for example, the industrial alkali lignin is derived from corn cobs.
In a specific embodiment, in step (1), the dropping rate of epichlorohydrin is 0.25 to 0.75mL/min, preferably 0.5mL/min. If the dropping speed is more than 0.75mL/min, the dropping speed is too fast, which can cause the lignin to agglomerate.
In a specific embodiment, in step (1), the mixed system is stirred and reacted at 40-60 ℃ for 7-9 hours, preferably at 50 ℃ for 8 hours.
In a specific embodiment, in step (1), the alkali solution is 0.2 to 1.5mol/L aqueous sodium hydroxide solution, most preferably 1mol/L. When the concentration of the alkali liquor is more than 1.5mol/L, a large amount of heat is released when the alkali liquor is prepared, so that the risk of an experiment is increased, and unnecessary medicine waste is generated; and when the concentration is less than 0.2mol/L, the dissolving capacity of the alkali solution to the alkali lignin is reduced, which is not beneficial to the subsequent reaction.
In a specific embodiment, in step (1), the concentration of alkali lignin in the alkali lignin solution is 0.1-0.5g/mL, more preferably 0.1-0.25g/mL, and most preferably 0.1g/mL. The concentration of the alkali lignin is higher than 0.5g/mL, so that the dissolving difficulty of the alkali lignin in the alkali liquor is increased, the viscosity of the alkali lignin solution is increased, the uniform mixing with reactants in the subsequent reaction is not facilitated, and the energy consumption of a reaction system is increased; when the concentration is less than 0.1g/mL, the content of alkali lignin in the system is too low, and the reaction efficiency is reduced.
In a specific embodiment, in the step (2), the temperature rise rate of the carbonization step is 10-15 ℃/min. The temperature rise speed exceeds 15 ℃/min, unnecessary load of the instrument is increased, and the danger is also increased; less than 10 deg.C/min, the required time is prolonged, and the energy consumption is increased.
In a specific embodiment, in the step (2), the inert gas is introduced at a rate ranging from 20 to 100mL/min; the speed of introducing inert gas exceeds 100mL/min, and the sample can be blown away when the gas flow speed in the tubular furnace is too high; and when the concentration is lower than 20mL/min, the gas generated during the amination lignin carbonization can not be removed completely in time.
In particular embodiments, in step (2), the target temperature range is 250-400 ℃, more preferably 300 ℃; the lignin skeleton structure is disintegrated to be an all-carbon structure at the temperature of over 400 ℃; the aminated lignin is difficult to ensure complete carbonization within a certain time at the temperature of less than 250 ℃.
In a specific embodiment, in step (2), the constant temperature time is 60 to 150 minutes, more preferably 120 minutes. The constant temperature time exceeds 150 minutes, which may cause excessive carbonization and increase energy consumption; and when the time is less than 60 minutes, the aminated lignin is difficult to ensure complete carbonization at a certain temperature.
In a specific embodiment, in step (3), the carbonized aminated lignin and CuCl 2 Is 5. The concentration of carbonized aminated lignin in N, N-dimethylformamide is 0.005-0.01g/ml, more preferably 0.008g/ml. Carbonized aminated lignin and CuCl 2 Higher than 5 2 Too much excessive solvent is used in subsequent washing, and unnecessary medicine waste is caused; less than 5 2 In an amount insufficient to form saturated Cu-N coordination bonds, providing Cu 2+ The possibility of binding oxygen is not favorable for the subsequent preservation of the sample. The concentration of carbonized aminated lignin in N, N-dimethylformamide exceeds 0.01g/ml, so that the amount of a solvent required in subsequent washing is increased, and the recovery of an organic solvent is difficult; below 0.005g/ml, too much solvent tends to exacerbate the requirements for containment equipment and increase production costs.
In a specific embodiment, in step (3), the heating temperature is 90-120 ℃, preferably 100-120 ℃, more preferably 110 ℃, and the constant temperature time is 8-11 hours.
In specific embodiments, in steps (1) and (3), the detergent is typically ethanol, acetone, or a mixture thereof.
In another aspect, the present invention provides a dye adsorbent prepared according to the above method.
In yet another aspect, the present invention provides a method of adsorbing a cationic dye in a solution, the method comprising using the dye adsorbent described above.
In the method, a dye adsorbent is added into a cationic dye solution, the mixture is stirred at a constant temperature until the adsorption is balanced, and the absorbance of the solution is measured after the mixture is filtered.
In particular embodiments, the cationic dye may include azure B, safranin T, methylene blue. The pH of the dye solution is 1 to 12, preferably 5 to 8, more preferably 6.5. The initial concentration of the cationic dye is 200-1800mg/L. The concentration of the dye adsorbent in the mixed solution is 0.5-2mg/mL, preferably 1mg/L. The dye adsorbent has better adsorption effect under alkaline condition, but in order to save cost, water (pH is about 6.5) is directly used as adsorption condition. The initial concentration of the cationic dye was 200-1800mg/L, within which a significant change in the adsorption effect could be observed. The concentration of the dye adsorbent in the mixed solution is less than 0.5mg/mL, and the adsorption effect is not obvious; more than 2mg/mL, causing unnecessary waste. For the convenience of calculation, the concentration of the dye adsorbent in the mixed solution was set to 1mg/mL.
In a particular embodiment, the reaction temperature in the process is 20 to 55 ℃, preferably 20 to 30 ℃. The temperature range is close to the room temperature or the body temperature, and the process cost is saved. The reaction time is 5 to 900 minutes, preferably 10 to 720 minutes. The reaction time is too long and exceeds the time for the adsorption to reach the equilibrium, so the cost is wasted; if the time is too short, the adsorption effect is not obvious.
In yet another aspect, the present invention provides a method for separating a dye, the method comprising using the above dye adsorbent.
In the method, an anionic dye and a cationic dye are mixed, the pH of a mixed solution is adjusted to be about 6.5, the mass concentration ratio of the anionic dye to the cationic dye is 1.
In a specific embodiment, the anionic dye methyl orange can be selected for the experiment. The total dye concentration is 50-200mg/L, preferably 100mg/L. The concentration of the adsorbent in the mixed solution is 0.5 to 2mg/mL, preferably 1mg/mL. The adsorption time is 0.5 to 5 minutes, preferably 1 minute. The total dye concentration is less than 50mg/L, and the dye is adsorbed indiscriminately; the total dye concentration is more than 200mg/L, and the dye adsorbent does not completely adsorb azure B and safranine T. The concentration of the dye adsorbent in the mixed solution is less than 0.5mg/mL, and the adsorption effect is not obvious; more than 2mg/mL, causing unnecessary waste. For convenience of calculation, the concentration of the dye adsorbent in the mixed solution was set to 1mg/mL. The adsorption time is less than 0.5 minute, and the adsorption to azure B and safranine T is incomplete; the adsorption time is greater than 5 minutes, at which concentration both dyes will be adsorbed.
In yet another aspect, the present invention provides a dye-adsorbing formulation comprising the above dye-adsorbent.
In yet another aspect, the present invention provides a dye separation formulation comprising the dye adsorbent described above.
Advantageous effects
The method adopts the methods of amination, carbonization and copper doping of alkali lignin to construct the dye adsorbent, has simple operation, rich raw materials, short preparation period and low overall cost, and is a novel, efficient and feasible method.
Specifically, compared with the prior art, the invention has the following advantages and beneficial effects:
(1) The invention constructs Cu-N on a lignin matrix x The stable structure of the method is used for preparing the dye adsorbent, and the method is a new method for widening the application range of lignin and the types of the dye adsorbents.
(2) The dye adsorbent prepared by the invention is Cu-N x The structure endows lignin with more adsorption sites, and can adsorb cationic dyes such as azure B, safranine T, methylene blue and the like in a large amount.
(3) The dye adsorbent prepared by the invention can quickly separate cationic dyes in a mixture of anionic dyes and cationic dyes.
Drawings
FIG. 1: SEM image (left) and SEM-EDS image (right) of the product of example 1 of the invention, wherein the SEM-EDS image shows the distribution of elements C, N, O and Cu respectively.
FIG. 2: the X-ray photoelectron spectrum of the product of example 1 of the present invention.
FIG. 3: (a) After the product of the example 1 of the invention and a sample not doped with copper are added into 500mg/L azure B, the absorbance of the solution changes with time (pH =6.5, the reaction temperature is room temperature, and the reaction time is 10 minutes); (b) The product obtained in the embodiment 1 of the invention has absorbance (reaction temperature is room temperature) of 12h after adding 800mg/L azure B with different pH values; (c) The adsorption capacity of the product of the invention example 1 on azure B changes with the temperature and the initial concentration of the dye (pH =6.5, reaction time 12 hours); adsorbing 800mg/L azure B by the product obtained in the embodiment 1 of the invention, (d) primary Pseudo fitting, (e) secondary Pseudo fitting, (f) intra-particle diffusion kinetics fitting curve (pH =6.5, reaction temperature is room temperature, and reaction time is 12 hours); the product of example 1 of the invention adsorbs azure B (g) Langmuir fitting, (h) Freundlich fitting (pH =6.5, reaction 12 hours); (i) The product obtained in the embodiment 1 of the invention has the selectivity coefficient on azure B under different mass concentration ratios of methyl orange to azure B.
FIG. 4: comparative optical photographs (pH =6.5, reaction 1 min) before and after addition of azure B (500 ppm) and a mixed solution of azure B (50 ppm) and methyl orange (50 ppm) to the product of inventive example 1.
Detailed Description
Hereinafter, preferred embodiments of the present disclosure will be described in detail with reference to the accompanying drawings. Before the description, it should be understood that the terms used in the specification and the appended claims should not be construed as limited to general and dictionary meanings, but interpreted based on the meanings and concepts corresponding to technical aspects of the present invention on the basis of the principle that the inventor is allowed to define terms appropriately for the best explanation. Accordingly, the description herein is of preferred examples for the purpose of illustration only and is not intended to limit the scope of the present invention, so it will be understood that other equivalent implementations and modifications may be made without departing from the spirit and scope of the present invention.
Term(s)
In this application, room temperature may refer to 25 ± 3 ℃.
The following examples are given by way of illustration of embodiments of the invention and are not to be construed as limiting the invention, and it will be understood by those skilled in the art that modifications may be made without departing from the spirit and scope of the invention.
The apparatus used in the following examples included: japanese SU8010 cold field emission scanning electron microscope, thermo ESCALAB 250XI and UV230011 ultraviolet visible spectrophotometer. Unless otherwise specified, reagents or other instruments and equipment used in the following examples are commercially available products.
Example 1
20g of industrial corncob alkali lignin powder was dissolved in 200mL of 1mol/L aqueous sodium hydroxide solution to obtain 0.1g/mL lignin solution. The solution was placed in a three-necked flask, and a condenser tube was placed above the flask to condense the solution. After the temperature is raised to 50 ℃, 5mL of epichlorohydrin is added into the alkali lignin solution drop by drop, the dropping speed is controlled to be about 0.5mL/min, and the dropping frequency is one second per drop. And stirring the reaction mixed system for 8 hours, dialyzing to be neutral, performing suction filtration, and performing vacuum drying at 40 ℃ to obtain the epoxidation intermediate. And adding the prepared epoxidation intermediate into a three-neck flask, dripping 20mL of triethylene tetramine, heating for reaction for 5 hours, filtering, washing with ethanol, and drying to obtain the aminated lignin.
And (3) putting the obtained aminated lignin into a quartz boat, heating to 300 ℃ at a speed of 10 ℃/min, keeping for 2 hours, and then cooling to room temperature to finish carbonization. 0.25g of the carbonized sample was taken out with a quartz tube, and 0.25g of CuCl was added 2 And 30mL of N, N-dimethylformamide are added into a hydrothermal reaction kettle and the hydrothermal reaction kettle is filled with N 2 Stirring for 10 hours at 110 ℃, cooling to room temperature, and washing with N, N-dimethylformamide and ethanol for multiple times to obtain a black product, namely the lignin-based dye adsorbent prepared from triethylene tetramine.
The molar mass of azure B is 306g/mol, the molecular size is
The sample can complete the adsorption of 500mg/L azure B in 10 minutes, and the adsorption rate is faster compared with the sample (80%) not doped with copper. The adsorption effect of this sample on azure B increases with increasing pH. At the same temperature, the adsorption effect of the sample on azure B is enhanced along with the initial concentration of the dye, and the adsorption saturation is kept equal.The increase in temperature favors the adsorption of azure B by the sample. The adsorption capacity of the sample on azure B obtained by the experiment is 1168mg/g. In addition, the adsorption process of azure B on the sample is more in line with the Pseudo second order equation (R) 2 = 1) and Langmuir equation (R) 2 = 1), belongs to single-layer adsorption, and the adsorption process is roughly divided into three sections of bulk diffusion, liquid film diffusion and intra-particle diffusion. The change in gibbs free energy Δ G at each temperature was negative, indicating that the adsorption process was spontaneous. The enthalpy change Δ H in the adsorption process was 7.45kJ/mol and the entropy change Δ S was 28.22kJ/mol, indicating that the process is a spontaneous endothermic reaction, the main force being chemical bonding. The molar mass of methyl orange is 327g/mol, and the molecular size is
In the mixed solution of methyl orange/azure B with different mass concentration ratios, the selectivity coefficient of the sample to the azure B is maximum (198) when the concentration ratio is 5, and the method can be used for the selective rapid separation of the azure B in the mixed dye at the concentration ratio of 5.
Example 2
This example was conducted in the same manner as example 1 except that the prepared dye adsorbent was used for adsorption and selective separation of safranin T, another cationic dye. The molar mass of safranine T is 351g/mol, and the molecular size is
The sample can complete the adsorption of 80% of safranin T of 500mg/L in 10 minutes, and compared with a sample (50%) not doped with copper, the adsorption rate is faster and the adsorption amount is larger. The adsorption effect of the sample on safranin T is enhanced with the increase of pH. At the same temperature, the adsorption effect of the sample on the safranine T is enhanced along with the initial concentration of the dye, and the adsorption saturation is achieved and then the adsorption effect is leveled. The temperature increase favors the adsorption of the safranin T by the sample. The adsorption capacity of this sample on safranin T obtained from the experiment was 1420mg/g. In addition, the adsorption process of the safranin T on the sample is more consistent with the Pseudo second-order equation (R) 2 = 1) and Langmuir equation (R) 2 = 1) belongs to single-layer adsorption, and the adsorption process is roughly divided into bulk diffusion and liquid membrane diffusionThree sections of powder and granules are diffused. The change in gibbs free energy Δ G at each temperature was negative, indicating that the adsorption process was spontaneous. The enthalpy change delta H in the adsorption process is 5.85kJ/mol, and the entropy change delta S is 29.08kJ/mol, which indicates that the process is a spontaneous endothermic reaction, and the main acting force is chemical bonding. The molar mass of methyl orange is 327g/mol, and the molecular size is
In methyl orange/safranin T mixed solutions with different mass concentration ratios, the selectivity coefficient of the sample to safranin T is maximum (32) when the concentration ratio is 5, and the method can be used for the selective and rapid separation of safranin T in the mixed dye at the concentration ratio.
Example 3
This example was conducted in the same manner as example 1 except that the prepared dye adsorbent was used for adsorption and selective separation of methylene blue of another cationic dye. The molar mass of methylene blue was 479g/mol, the molecular size was
The sample can complete the adsorption of 80% of methylene blue of 500mg/L in 10 minutes, and compared with a sample (50%) not doped with copper, the adsorption rate is faster and the adsorption amount is larger. The adsorption effect of the sample on methylene blue is enhanced with the increase of the pH. At the same temperature, the adsorption effect of the sample on methylene blue is enhanced along with the initial concentration of the dye, and the adsorption saturation is achieved and then the adsorption effect is leveled. The temperature increase favors the adsorption of methylene blue by the sample. The adsorption capacity of this sample on methylene blue obtained by the experiment was 787mg/g. In addition, the adsorption process of methylene blue on the sample is more consistent with the Pseudo second-order equation (R) 2 = 0.9998) and Langmuir equation (R) 2 = 0.9999), belongs to single-layer adsorption, and the adsorption process is roughly divided into three sections of bulk diffusion, liquid film diffusion and intra-particle diffusion. The change in gibbs free energy Δ G at each temperature was negative, indicating that the adsorption process was spontaneous. The enthalpy change delta H in the adsorption process is 1.921kJ/mol, the entropy change delta S is 3.026kJ/mol, which shows that the process is a spontaneous endothermic reaction, and the main acting force is a chemical bondAnd (6) mixing. The molar mass of methyl orange is 327g/mol, and the molecular size is
In the mixed solution of methyl orange/methylene blue with different mass concentration ratios, the selectivity coefficient of the sample to the methylene blue is maximum (103) when the concentration ratio is 5, and the method can be used for the selective rapid separation of the methylene blue in the mixed dye at the concentration ratio.
It can be seen from comparison among examples 1, 2 and 3 that the lignin-based dye adsorbent obtained by the invention can adsorb a large amount of cationic dyes including azure B, safranine T and methylene blue, and the smaller the molecular size of the dye is, the stronger the selectivity of the dye adsorbent to the cationic dyes in a cationic and anionic dye mixed system is.
The above examples are only intended to illustrate the technical solution of the present invention and not to limit it; the description proposed herein is just a preferable example for the purpose of illustrations only, not intended to limit the scope of the invention, so it should be understood that various changes in the detailed description of the invention or equivalent substitutions for parts of technical features may be made without departing from the spirit and scope of the invention, which should be construed to cover the technical scope of the invention as claimed.
Claims (10)
1. A method for preparing a copper ion doped aminated lignin-based cationic dye adsorbent, comprising the steps of:
(1) Preparing aminated lignin:
the aminated lignin can be purchased from the market or manufactured by self, if the self-manufacture adopts the following steps: dissolving alkali lignin in an alkali solution to obtain an alkali lignin solution, dropwise adding epoxy chloropropane into the alkali lignin solution, reacting a mixed system, dialyzing to be neutral, filtering, and drying to obtain an epoxidation intermediate; adding polyamine dropwise into the prepared epoxidation intermediate, heating for reaction, filtering, washing with a detergent, and drying to obtain aminated lignin;
(2) Carbonizing:
carbonizing the aminated lignin obtained in the step (1);
(3) Copper doping:
the carbonized aminated lignin obtained in the step (2) is mixed with N, N-Dimethylformamide (DMF) and copper dichloride (CuCl) 2 ) Mixing, heating to react under the protection of inert gas, washing with a detergent, and drying to obtain a product, namely the dye adsorbent.
2. The method of claim 1, wherein the first and second light sources are selected from the group consisting of,
wherein, in the step (1), the alkali lignin is industrial alkali lignin, for example, the industrial alkali lignin is from corncobs, the alkali solution is 0.2-1.5mol/L sodium hydroxide aqueous solution, and the concentration of the alkali lignin in the alkali lignin solution is 0.1-0.5g/mL. The dripping speed of the epichlorohydrin is 0.25-0.75mL/min, the mixed system is stirred and reacts for 7-9 hours at the temperature of 40-60 ℃, and the polyamine is triethylene tetramine.
3. The method of claim 1, wherein the first and second light sources are selected from the group consisting of,
wherein in the step (2), the temperature rise speed in the carbonization process is 10-15 ℃/min, the speed range of introducing inert gas is 20-100mL/min, the target temperature range is 250-400 ℃, and the constant temperature time is 60-150 minutes.
4. The method as set forth in claim 1, wherein,
wherein, in the step (3), the carbonized aminated lignin and CuCl are 2 The mass ratio of (1) to (5) is as follows, the concentration of the aminated lignin in N, N-dimethylformamide is 0.005g/ml to 0.01g/ml, the reaction temperature is 90-120 ℃, and the constant temperature time is 8-11 hours.
5. The method of claim 1, wherein the first and second light sources are selected from the group consisting of,
wherein, in the steps (1) and (3), the used detergent is any one of ethanol, acetone or a mixed solution of the ethanol and the acetone.
6. A dye adsorbent prepared according to the method of any one of claims 1-5.
7. A method of adsorbing a cationic dye in a solution, the method comprising using the dye adsorbent of claim 6.
8. The method according to claim 7, wherein in the method, the dye adsorbent according to claim 6 is added to a cationic dye solution, stirred at a constant temperature until adsorption equilibrium, and the absorbance of the solution is measured after filtration.
9. A method of separating mixed dyes, the method comprising using the dye adsorbent of claim 6.
10. The method according to claim 9, wherein in the method, an anionic dye and a cationic dye are mixed, the pH of the mixed solution is adjusted to 6.5 to 7.5, the mass concentration ratio of the anionic dye to the cationic dye is 1 to 9, the dye adsorbent according to claim 6 is added, the mixed solution is filtered after constant temperature adsorption, and the scanning of absorbance is performed.
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